WO2023214656A1 - Composition d'électrolyte aqueux et batterie secondaire aqueuse comprenant cette dernière - Google Patents

Composition d'électrolyte aqueux et batterie secondaire aqueuse comprenant cette dernière Download PDF

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Publication number
WO2023214656A1
WO2023214656A1 PCT/KR2023/002891 KR2023002891W WO2023214656A1 WO 2023214656 A1 WO2023214656 A1 WO 2023214656A1 KR 2023002891 W KR2023002891 W KR 2023002891W WO 2023214656 A1 WO2023214656 A1 WO 2023214656A1
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aqueous electrolyte
additive
electrolyte composition
group
aqueous
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PCT/KR2023/002891
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English (en)
Korean (ko)
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이호춘
이석형
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재단법인대구경북과학기술원
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Publication of WO2023214656A1 publication Critical patent/WO2023214656A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes

Definitions

  • Various embodiments of the present invention relate to an aqueous electrolyte composition and an aqueous secondary battery containing the same. Specifically, various embodiments of the present invention relate to an aqueous electrolyte composition containing two types of additives that perform different functions, and an aqueous secondary battery containing the same.
  • aqueous secondary batteries use an aqueous electrolyte instead of a flammable organic electrolyte, they can fundamentally solve the safety issues of secondary batteries, and do not require strict moisture management in the manufacturing process, so they have relatively high price competitiveness.
  • aqueous electrolytes have the disadvantage of being more easily oxidized/reduced and decomposed compared to organic electrolytes.
  • the charging voltage of aqueous secondary batteries is limited ( ⁇ 2 V), which has a significant disadvantage in that the energy density is significantly lower than that of existing secondary batteries.
  • WiSE the reduction and decomposition of anions is promoted, and a protective film (solid electrolyte interphase, SEI) is easily formed on the cathode surface, and this SEI suppresses additional water reduction and decomposition reaction (Hydrogen elevolution reaction, HER). Additionally, due to the low activity of water in WISE, the oxygen evolution reaction (OER) of water at the anode is suppressed. Therefore, it was reported that the charging voltage of water-based secondary batteries using WiSE was significantly increased (> 2V).
  • SEI forming the WISE group is mainly composed of inorganic components (LiF, Li 2 O, Li 2 CO 3 , etc.), and this inorganic SEI shows high electrical insulation and excellent HER inhibition effect.
  • SEI an inorganic component, has a problem of being easily dissolved and lost in electrolyte due to its high solubility in aqueous solution.
  • solubility of inorganic components further increases, making the problem of dissolution/disappearance of SEI more serious.
  • WiBSE Water-in-Bisalt Electrolyte
  • aqueous and non-aqueous aqueous hybrid electrolyte
  • WiBSE and hybrid electrolytes can somewhat alleviate the SEI dissolution/dissipation issue, but are not a sufficient solution. Moreover, as the salt concentration of WiBSE and the hybrid electrolyte increases and the organic solvent is introduced, the rate of ion transfer in the electrolyte decreases significantly, resulting in a decrease in the rate capability of the secondary battery. Additionally, there is a problem of increased material costs.
  • Various embodiments of the present invention have been developed to solve the above-described problems, and the object is to provide an aqueous electrolyte composition that can dramatically improve the performance of an aqueous secondary battery and an aqueous secondary battery containing the same.
  • the aqueous electrolyte composition includes a first additive, a second additive, and an aqueous electrolyte, and the first additive and the second additive have different reduction reaction potentials.
  • Aqueous secondary batteries according to various embodiments of the present invention may include the aqueous electrolyte composition described above.
  • the present invention is expected to form a double-layer SEI layer by mixing two types of additives in an aqueous electrolyte composition, and this double-layer SEI layer blocks HER and minimizes dissolution/dissipation of SEI, thereby achieving high capacity of aqueous secondary batteries. Maintenance rate, remaining capacity ratio, and coulombic efficiency can be implemented.
  • FIG. 1 is a schematic diagram of an aqueous secondary battery including an aqueous electrolyte composition according to an embodiment of the present invention.
  • FIG. 2 shows the electrochemical stability window (ESW) measurement results of the aqueous electrolyte compositions according to Example 1 and Comparative Examples 1 to 3 of the present invention through cyclic voltammetry (CV) measurement.
  • ESW electrochemical stability window
  • Figure 3 shows room temperature charge/discharge results and Coulombic efficiency measurement results of LMO/LTO batteries using the aqueous electrolyte compositions of Example 1 and Comparative Examples 1 to 3.
  • the aqueous electrolyte composition according to various embodiments of the present invention may include a first additive, a second additive, and an aqueous electrolyte.
  • the first additive may be a compound that forms radicals through an electrochemical reduction reaction.
  • the first additive may be at least one selected from the group consisting of persulfate-based compounds, peroxide-based compounds, and AZO-based compounds.
  • PPS Potassium persulfate
  • APS Ammonium persulfate
  • SPS Sodium persulfate
  • Peroxide-based compounds include Lauroyl Peroxide (LPO), Benzoyl Peroxide (BPO), t-butyl Peroxy-2-ethylhexanoate (BPEH), and 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, as shown in Table 2 below.
  • TBPB peroxybenzoate
  • APEH t-amylperoxy-2-ethylhexanoate
  • TBPO tert-Butylperoxide
  • TAPP tert-Amylperpivalate
  • DTBD Di-tert-butyl diperoxyoxalate
  • TBHP tert-butyl hydroperoxide
  • TBPB peroxybenzoate
  • Azo-based compounds include 2,2'-Azobis (2,4-dimethyl valronitrile (V65), Azobisisobutyronitrile (AIBN), 4,4'-Azobis(4-cyanovaleric acid) (ABCA), and 1, as shown in Table 3 below. It may be at least one of 1' Azobis(cyclohexanecarbonitrile)(ABCH).
  • the second additive is capable of electrochemical reduction polymerization and may be a polymer monomer containing a hydrophobic functional group.
  • the second additive may be a compound of the A+B structure, where A is a polymerizable functional group responsible for polymerization reaction, and B may be a hydrophobic functional group. That is, the second additive may have a polymerizable functional group and a hydrophobic functional group.
  • the polymerizable functional group may be an acrylic group or a methacryl group
  • the hydrophobic functional group may be at least one selected from the group consisting of fluorine-substituted linear alkyl, cyclic alkyl, alkyne, and alkenyl group.
  • the second additive is 2,2,2-Trifluoroethyl methacrylate (TFEMA), 2,2,2-Trifluoroethyl acrylate (TFEA), 1,1,1,3,3,3-Hexafluoroisopropyl as shown in Table 4 below.
  • TFEMA 2,2,2-Trifluoroethyl methacrylate
  • TFEA 2,2,2-Trifluoroethyl acrylate
  • Table 4 1,1,1,3,3,3-Hexafluoroisopropyl as shown in Table 4 below.
  • HFPMA 2,2,3,4,4,4-Hexafluorobutyl methacrylate
  • HBMA 2,2,3,3-Tetrafluoropropyl methacrylate
  • TFPMA 2,2,3,3,4,4,5 ,5-Octafluoropentyl acrylate
  • OFPA 2,2,3,3,4,4,4-Heptafluorobutyl methacrylate
  • PFPMA 2,2,3,3,3-Pentafluoropropyl methacrylate
  • DDFH 1,1,1,3,3,3-Hexafluoroisopropyl acrylate
  • PFPA Pentafluorophenyl acrylate It may include any one selected from the group.
  • Each of these first and second additives may be included in an amount of 0.01 wt% to 3 wt% based on the entire aqueous electrolyte composition.
  • the HER inhibition effect of the aqueous electrolyte composition can be maximized and the dissolution or loss of SEI can be minimized.
  • the reduction reaction potential of the first additive and the second additive may be different from each other. Specifically, the reduction reaction potential of the first additive is higher than the reduction reaction potential of the second additive, so that the reduction reaction of the first additive may occur first at the cathode.
  • the internal SEI of the inorganic component effectively inhibits electron transfer due to the high electrical insulation properties of the inorganic material, thereby suppressing the reduction reaction of additional electrolytes.
  • the external SEI of the hydrophobic polymer component effectively inhibits the access and penetration of free water molecules, and can block the internal SEI of the inorganic component from dissolving or disappearing into the electrolyte. In this way, through the synergistic effect between two types of additives that play different roles, it is possible to simultaneously achieve HER inhibition and dissolution/dissipation inhibition effects.
  • water-based electrolytes include high-concentration water-based electrolyte (Water-in-Salt Electrolyte, WiSE) using an excess of salt, WiBSE (Water-in-Bisalt Electrolyte) using a mixture of two types of salt, and hybrid using an organic compound as a cosolvent. It may be at least one of electrolytes.
  • WiSE Water-in-Salt Electrolyte
  • WiBSE Water-in-Bisalt Electrolyte
  • organic compound as a cosolvent. It may be at least one of electrolytes.
  • the MX concentration may have an MX/H 2 O molar ratio of 1/10 to 1/2.
  • the aqueous electrolyte may contain an organic compound as a cosolvent.
  • the organic compound may be, for example, any one of dimethyl sulfoxide, sulfolane (SL), acetonitrile, and trimethyl phosphate.
  • the content of the organic compound may be in a water/organic solvent molar ratio of 1/10 to 10/1.
  • the positive electrode active materials for aqueous secondary batteries are LiMn 2 O 4 , LiCoO 2 , LiFePO 4 , LiNi ) 3 , K 3 V 2 (PO 4 ) 3 , Prussian blue and its derivatives, conductive polymers, or radical polymers may be used, but are not limited to these.
  • the anode active material of an aqueous secondary battery may be Li 4 Ti 5 O 12 , TiO 2 , WO 3 , Sulfur, Aluminum, or carbon material, but is not limited to these.
  • An aqueous electrolyte composition was prepared with the composition shown in Table 5 below.
  • Example 1 To compare the ESW of the electrolyte compositions prepared in Example 1 and Comparative Examples 1 to 3 according to Table 1, a three-electrode system (Glassy carbon working electrode, Ag/AgCl reference electrode, and Pt auxiliary electrode) was used, Cyclic voltammetry (CV) measurements were performed in the Open Circuit Voltage -2.0 V region at a scanning rate of 10 mV/s. The first scan direction started in the reduction potential direction.
  • CV Cyclic voltammetry
  • the reduction current observed between -1.5 V and -2.0 V is due to the reduction decomposition reaction (HER) of water, and the size of the reduction current is proportional to the degree of HER.
  • Comparative Example 2 In the case of Comparative Example 2, in which 1 wt% PPS was introduced, a small reduction peak was observed in the 0 V to 0.5 V region of the first cycle, and thereafter, the reduction current in the -1.5 V to -2.0 V region significantly decreased compared to Comparative Example 1. You can see that it was done. This can be assumed to be because SEI was formed on the electrode surface as a result of the reduction reaction of the PPS additive (0 V to 0.5 V region), and this SEI suppressed the HER of WiSE.
  • Example 1 where 1 wt% of PPS and DDFH were each introduced, the reduction current was most significantly reduced compared to Comparative Example 1, as well as 2 or 3 in which PPS or DDFH additives were used alone. In other words, it can be seen that by using two additives simultaneously, the HER reaction can be more effectively suppressed and the ESW of the electrolyte can be expanded.
  • a coin-type battery was manufactured using electrolyte, LiMn 2 O 4 (LMO) anode, Li 4 Ti 5 O 12 (LTO) anode, and glass fiber separator.
  • the manufactured battery was charged and discharged in the range of 2.0 to 2.7 V at room temperature (25°C) at a constant current of 1 C.
  • Example 1 The room temperature charge/discharge lifespan results of LMO/LTO batteries using WiSE of Example 1 and Comparative Examples 1 to 3 are shown in FIG. 3.
  • the capacity retention ratio defined as the ratio of the discharge capacity after 500 charging and discharging compared to the initial capacity, is presented in Table 5 below.
  • the battery using the electrolyte composition of Example 1 showed a high capacity of more than 100 mAhg -1 after charging and discharging 500 times, while the battery using the electrolyte composition of Comparative Examples 1 to 3 showed serious deterioration.
  • Table 5 the capacity maintenance rate after charging and discharging 500 times decreased in the order of Example 1 > Comparative Example 2 > Comparative Example 3 > Comparative Example 1.
  • Example 2 Comparative Example 5 > Comparative Example 6 > Comparative Example 4.
  • batteries to which the two additives were applied together showed better lifespan characteristics than batteries to which each additive was applied alone, as well as batteries to which no additives were applied.
  • Example 3 and Comparative Examples 7 to 9 LMO/LTO batteries using the hybrid electrolyte were evaluated in the same manner as in the previous case (2-1), and the capacity retention rates after 500 charge and discharge are presented in Table 5.
  • the capacity maintenance rate was in the following order: Example 3 > Comparative Example 8 > Comparative Example 9 > Comparative Example 7.
  • batteries to which the two additives were applied together showed better lifespan characteristics than batteries to which each additive was applied alone, as well as batteries to which no additives were applied.
  • Example 1 LMO/LTO batteries using the electrolytes of Examples 4 to 6, in which only PPS was replaced with SPS, BPEH, and ABCA in the electrolyte, were evaluated in the same manner as in the previous case (2-1), and the capacity retention rate after 500 charge and discharge is presented in Table 5.
  • Example 1 There was no significant difference in capacity retention rate between Example 1 and Examples 4 to 6. In this way, similar characteristics can be achieved by changing the cation of Persulfate to Na+ or using Peroxide or Azo-based compounds instead of Persulfate. That is, it can be seen that compounds that undergo reduction decomposition to form radicals can be used as the first additive.
  • Example 7 and Example 1 showed similar capacity maintenance rates. Comparative Example 10 showed a significantly low capacity maintenance rate. In other words, it can be seen that the presence or absence of a hydrophobic functional group has a significant impact on battery performance.
  • the LMO/LTO battery manufactured in the same way as in the room temperature lifespan evaluation was charged and discharged three times in the 2.0 to 2.7 V range at 1 C constant current at room temperature (25°C), and then the battery in a fully charged (SOC 100) state was stored at 60°C. It was preserved for 1 day. Afterwards, the residual capacity ratio, defined as the ratio of the remaining capacity compared to the capacity before high-temperature preservation, is presented in Table 5.
  • Example 1 Comparative Example 2 > Comparative Example 3 > Comparative Example 1.
  • batteries to which the two additives were applied together showed better high-temperature preservation characteristics than batteries to which each additive was applied alone, as well as batteries to which no additives were applied.
  • Example 1 The remaining capacity ratio did not show a significant difference between Example 1 and Examples 4 to 6.
  • Example 7 and Example 1 showed similar remaining capacity ratios, but Comparative Example 10 showed a significantly lower remaining capacity ratio.
  • the present invention relates to an aqueous electrolyte for an aqueous secondary battery containing two types of additives. It is expected to form a double-layer SEI layer by mixing the two types of additives in the electrolyte, and block HER through this double-layer SEI layer. By minimizing the dissolution/dissipation of SEI, high capacity retention rate, remaining capacity ratio, and coulombic efficiency can be realized, making it highly industrially usable.

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Abstract

La composition d'électrolyte aqueux selon divers modes de réalisation de la présente invention comprend un premier additif, un second additif et un électrolyte aqueux, le premier additif et le second additif étant différents l'un de l'autre en termes de potentiel de réaction de réduction. La batterie secondaire aqueuse selon divers modes de réalisation de la présente divulgation peut comporter la composition d'électrolyte aqueux susmentionnée.
PCT/KR2023/002891 2022-05-06 2023-03-03 Composition d'électrolyte aqueux et batterie secondaire aqueuse comprenant cette dernière WO2023214656A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9461348B2 (en) * 2011-11-09 2016-10-04 Electricite De France Aqueous electrolyte for lithium-air battery
JP2019046589A (ja) * 2017-08-30 2019-03-22 トヨタ自動車株式会社 水系電解液及び水系リチウムイオン二次電池
KR20200013865A (ko) * 2018-07-31 2020-02-10 주식회사 엘지화학 수계 전해질 및 이를 포함하는 전기화학소자
KR20200053186A (ko) * 2018-11-08 2020-05-18 한국전기연구원 고온특성 향상을 위한 첨가제가 적용된 수계 전해액을 포함하는 단위 셀 및 이를 이용하는 에너지 저장 디바이스
KR20210035646A (ko) * 2019-09-24 2021-04-01 주식회사 엘지화학 전해질용 첨가제, 이를 포함하는 전해질 및 에너지 저장 디바이스

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9461348B2 (en) * 2011-11-09 2016-10-04 Electricite De France Aqueous electrolyte for lithium-air battery
JP2019046589A (ja) * 2017-08-30 2019-03-22 トヨタ自動車株式会社 水系電解液及び水系リチウムイオン二次電池
KR20200013865A (ko) * 2018-07-31 2020-02-10 주식회사 엘지화학 수계 전해질 및 이를 포함하는 전기화학소자
KR20200053186A (ko) * 2018-11-08 2020-05-18 한국전기연구원 고온특성 향상을 위한 첨가제가 적용된 수계 전해액을 포함하는 단위 셀 및 이를 이용하는 에너지 저장 디바이스
KR20210035646A (ko) * 2019-09-24 2021-04-01 주식회사 엘지화학 전해질용 첨가제, 이를 포함하는 전해질 및 에너지 저장 디바이스

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